Water soluble adduct of hydroxymethyl phosphorous compound and ammonia or amine compound and method of preparation

ABSTRACT

Soluble adduct polymers were allowed to react with phenol, alkyl substituted phenols or halogen substituted phenols which contain one or more hydrogens ortho or para to the phenolic hydroxyl group to (a) prepare flame resistant polymers and (b) prepare flame-, glow-, wrinkle- and shrink-resistant woven and knit textiles which contain 25% or more cellulosic fibers.

This is a division of application Ser. No. 499,804, filed Aug. 22, 1974now U.S. Pat. No. 3,953,166.

This invention relates to new phosphorus, nitrogen, and halogencontaining polymers and to their use in the production offlame-resistant organic fibrous materials. More specifically, it dealswith the reaction of adduct polymers with phenol or substituted phenolsto produce insoluble polymers and flame-resistant organic fibrousproducts when these insoluble polymers are found in or on the fibrousmaterials.

As employed throughout the specifications and claims of this invention,the term "adduct polymer" refers to the product formed by solubilizingunoxidized phosphorus- and nitrogen-containing polymers in solutionscontaining formaldehyde and an acid. The chemistry involved in thesolution of these polymers by the addition of formaldehyde and an acidis not known, but it is believed that chemical reactions occur whichmodify the polymers by altering the chain length and/or by addition ofthe reactants to the polymer or products therefrom.

The abbreviation THP refers to the compound tris (hydroxymethyl)phosphine, (HOCH₃)P. The term tetrakis (hydroxymethyl)phosphonium saltrefers to that class of compounds in which four hydroxymethyl groups arebonded to a phosphorus atom which is in the phosphonium state, thushaving a plus charge associated with it and the anion can be the anionof any organic or inorganic acid such as acetic, oxalic hydrochloric orphosphoric. The abbreviation Thpc refers to the compoundtetrakis(hydroxymethyl)phosphonium chloride. The termtetrakis(hydroxymethyl)phosphonium hydroxide or THPOH refers to asolution prepared by neutralizing any tetrakis(hydroxymethyl)phosphoniumsalt with any suitable base, inorganic or organic, such as sodiumhydroxide or triethanolamine.

Copending application filed of even date, Ser. No. 499,807, filed Aug.22, 1974, now U.S. Pat. No. 3,975,560 relates to the production and useof soluble adduct polymers and to the use of these polymers with certainnitrogenous compounds for the treatment of organic fibrous materials ineither a heat cure or chemical cure procedure for the production offlame-resistant organic fibrous textiles.

Copending application filed of even date, Ser. No. 499,806, filed Aug.22, 1974, now U.S. Pat. No. 3,961,110 relates to the product of adductpolymer solutions and the use of these polymers with phenols,substituted and unsubstituted phenols for the treatment of organicfibrous materials for the production of flame resistant organic fibrousmaterials. These adduct polymer solutions were prepared by the use ofphosphine polymers, formaldehyde, and a hydroxymethyl phosphonium salt.

Copending application filed of even date, Ser. No. 499,803, filed Aug.22, 1974, now U.S. Pat. No. 3,953,165 relates to the use of adductpolymer solutions and to the use of these solutions with certainnitrogenous compounds for the treatment of organic fibrous materials ineither a heat cure or chemical cure procedure for the production offlame resistant organic fibrous textiles. These solutions were preparedby the use of phosphine polymers, formaldehyde, and ahydroxymethylphosphonium salt.

A primary object of the present invention is to produce thermosettingflame-resistant polymers and flame-resistant organic fibrous materials.

Polymers of various types can be prepared by reactingtetrakis(hydroxymethyl)phosphonium salts, tris (hydroxymethyl)phosphineor tetrakis(hydroxymethyl)phosphonium hydroxide with ammonia or diaminessuch as ethylene diamine and 1,6-hexamethylenediamine orhexamethylenetetramine.

We have discovered that these adduct polymers react with phenol andsubstituted phenols, including halogenated phenols, which contain one ormore hydrogen atoms attached to ring carbons at the ortho or parapositions to the phenolic hydroxyl group to produce thermosettingflame-resistant polymers.

More specifically, the products and processes of our invention may bedescribed as follows: (1) Insoluble polymers are prepared by reactingTHP (with or without added formaldehyde) with ammonia, diamines, orhexamethylenetetramine or mixtures of these. Insoluble polymers may alsobe prepared by utilizing tetrakis(hydroxymethyl)phosphonium salts orhydroxide in lieu of THP. The mole ratio may vary from 1:4 to 4:1 ofamine to phosphorus compound. The preferred mole ratio is 1:1 with THPand tetrakis(hydroxymethyl)phosphonium hydroxide and 2:1 withtetrakis(hydroxymethyl)phosphonium chloride. (2) To produce clearsolutions of these polymers the polymer is mixed with formalin solutionand an acid. The ratio of formaldehyde added to phosphorus contained inthe polymer can vary from 1:4 to 4:1. The preferred ratio is 1:1. Theratio of acid added to the phosphorus contained in the polymer can varyfrom 1:10 to 2:1. The preferred ratio is 1:2. (3) The phenolic orhalogen substituted phenolic compound is allowed to react with theadduct polymer to produce thermosetting polymers in accordance with thisinvention. The reaction is carried out by dissolving the phenolic orhalogen substituted phenolic compound in a suitable medium, adding thissolution to a solution containing the adduct polymer and then heating asneeded until a viscous solution and finally a polymer is produced.Polymers produced by this process are insoluble, thermosetting and flameresistant. (4) To produce flame resistant organic textiles, the textilestructure is wetted with a solution containing the adduct polymer andthe phenolic or halogenated phenolic compound which contains one or morehydrogens ortho or para to the phenolic hydroxyl group, then drying andheating the textile at a temperature ranging from 90° to 170° C for aperiod of time necessary to promote copolymerization of the adductpolymer and the phenolic or halogenated phenolic compound within or onthe textile structure.

Phenolic compounds suitable for use in making the copolymers of thisinvention include phenol, o-cresol, m-cresol, p-cresol, catechol,resorcinol, hydroquinone and phloroglucinol. Halogenated phenoliccompounds suitable for use in making the copolymers of this inventioninclude o-bromophenol, m-bromophenol, p-bromophenol, o-phenetole,halophenylphenols and haloresorcinols. The primary requirement for thephenolic or halogenated phenolic compound is that it contain at leastone hydrogen attached to a ring carbon atom which is ortho or para tothe phenolic hydroxyl group. The preferred relative amounts of polymersadduct and phenolic compound used to copolymerize can be calculated byassuming one mole of phosphorus which is contained in the adduct polymerreacts with one mole of the phenolic compound. Polymers produced inaccordance with this invention contain phosphorus in the trivalent stateand this atom can be oxidized with oxidants such as peroxides,perborates and peracids to the phosphine oxide (pentavalent state).

Suitable solvents for preparing solutions of the phenolic or halogenatedphenolic compounds include water, methanol, ethanol, isopropanol andmixtures of these compounds.

Virtually any fibrous organic products capable of being impregnated withthe soluble adduct can be made flame resistant by use of this invention.Textiles suitable for use in this invention are woven, knit, or nonwovenstructures. For best results, the textile structure should contain atleast about 25% of a cellulosic fiber. Cellulosic fibers suitable foruse in this invention include, cotton, rayon, ramie, flax, and the likefibers. Various noncellulosic natural fibers can also be used in thisinvention, such as wool and mohair. Noncellulosic synthetic fiberssuitable for use in this invention along with a cellulosic fiber arepolyesters, nylons, acrylics, polyvinylchloride, and the like fibers.When cellulosic fibers are blended with flammable noncellulosic fibersit is preferable to have about 50% or more cellulosic fiber in the blendstructure.

The following examples illustrate but do not limit the scope of thisinvention.

EXAMPLE 1

The polymers were prepared by reacting the appropriate phosphoruscompound with the amine or diamine as described in Table I. All of thepolymers were filtered from the mother liquor, washed with water,ethanol and methanol before leaving to air dry for eight days. Thepolymers were then bottled and used to prepare the adduct polymers. InTable II the preparation of the adduct polymer from formaldehyde, acidand polymer are described. The adduct polymers were then mixed with thephenolic or halogenated phenolic compound in an appropriate solvent asdescribed in Table III. These solutions were used to (a) preparethermosetting polymers and (b) produce flame-resistant organic fibrousmaterials. Aliquots of the copolymer solutions were heated from about120°-150° C to produce thermosetting polymers which are described inTable IV. To produce flame-resistant organic fibrous materials, thetextile structures were impregnated with the solutions described inTable III, then heated to produce insoluble polymers in or on thefibrous structure. In Table V are shown in the fibrous materialstreated, the solutions of Table III used to treat the fibrous materialand a brief description of the product.

                  TABLE I                                                         ______________________________________                                        Phosphine Polymers                                                            Polymer No.                                                                             Reactants         % in Polymer                                      ______________________________________                                        1        1500g. 40% THPOH                                                              (Thpc neutralized with                                                                           31.8                                                       sodium hydroxide); 205g.                                                      ammonium hydroxide                                                            (29% ammonia)                                                        2        238g. Thpc (80%);                                                             238g Water; 175g   23.4                                                       ammonium hydroxide                                                            (29% ammonia)                                                        3        160g. THP (80%);   29.9                                                       200g water;                                                                   105g Hexamethylenetetramine                                          4        430g. 40% THPOH    35.4                                                       (Thpc neutralized with                                                        sodium hydroxide);105g.                                                       hexamethylenetetramine                                               5        573g. 40% THPOH    29.5                                                       (Thpc neutralized with                                                        sodium hydroxide);                                                            61.2g. ethylenediamine (98%)                                         6        573g 40% THPOH     21.5                                                       (Thpc neutralized with sodium                                                 hydroxide); 162g.                                                             1,6-hexamethylene diamine                                                     (70%)                                                                ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Soluble Adduct Polymers                                                       Description of                                                                Adduct                       Time Required                                    Polymer                      for Complete                                     Solution   Reactants         Solution                                         ______________________________________                                        A         120g Polymer No. 1;                                                                              4 hours                                                    30g Acetic Acid; 74.4g                                                        Formalin (37.5%);                                                             75.6g water                                                         B         40g. Polymer No. 2;                                                                              4 hours                                                    24.2g Formalin (37.5%);                                                       10.3g Phosphoric acid                                                         (H.sub.3 PO.sub.4) (85%);                                                     25.5g water                                                         C         40g Polymer No. 3; 4 hours                                                    30.8g. formalin                                                               (37.5%);                                                                      19.2g hydrochloric acid                                                       (HCl) (37%);                                                                  10g water                                                           D         43.8g Polymer No. 4;                                                                             4 hours                                                    11.2g oxalic acid;                                                            40g formalin (37.5%);                                                         14.5g water                                                         E         40g polymer No. 5; 24 hours                                                   10g acetic acid;                                                              25g formalin (37.5%);                                                         25g water                                                           F         40g. polymer No. 6;                                                                              100 hours                                                  10g Phosphoric Acid (H.sub.3 PO.sub.4)                                        25g formalin (37.5%);                                                         65g water                                                           ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Copolymer Solutions                                                           Designation                                                                   of Copolymer Solution                                                                         Composition of Solution                                       ______________________________________                                        G               20g of Soln. A; 6g water;                                                     10g ethanol; 4g phenol                                        H               20g of Soln. A; 6g water,                                                     10g ethanol; 4g m-bromophenol                                 I               25g of Soln. C; 10g water,                                                    10g ethanol; 5g bromo-                                                        hydroquinone                                                  J               25g of Soln. D; 10g water,                                                    10g ethanol; 5g phenol                                        K               25g of Soln E; 20g ethanol;                                                   5g metabromophenol                                            ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        Production of Flame Resistant Thermosetting Polymers                          Through Use of Adduct Polymers and Phenols                                                    Description of Thermosetting                                                  Polymer Resulting From                                                        Heating the Copolymer                                         Copolymer Solution Used                                                                       Solution from about 120-150° C                         (Designation from Table III)                                                                  for about 1-10 minutes                                        ______________________________________                                        G               Clear yellow, hard polymer,                                                   insoluble in water and ethanol.                                               Flame and glow resistant.                                                     Contains nitrogen and phosphorus.                             H               Clear yellow, hard polymer,                                                   insoluble in water and ethanol.                                               Flame and glow resistant.                                                     Contains nitrogen and phosohorus.                             I               Clear yellow hard polymer,                                                    insoluble in water and ethanol.                                               Flame and glow resistant.                                                     Contains nitrogen and phosphorus.                             J               Clear yellow hard polymer,                                                    insoluble in water and ethanol.                                               Flame and glow resistant.                                                     Contains nitrogen and phosphorus.                             K               Clear gold hard polymer,                                                      insoluble in water and                                                        ethanol. Flame and glow                                                       resistant. Contains nitrogen                                                  and phosphorus.                                               ______________________________________                                    

                                      TABLE V                                     __________________________________________________________________________    Preparation of Flame Resistant Organic Fibrous Materials                                             Approximate                                                     Adduct or                                                                           Conditions                                                                            Add-on of                                                       Copolymer                                                                           for Depositing                                                                        Retardant                                                                              Properties of Treated Fabric                           Solution                                                                            Insoluble                                                                             After Washing        Match                                      Applied to                                                                          Polymer in                                                                            the Treated          Test                              Fabric Treated                                                                         Fabric                                                                              Fabric  Textile Hand                                                                              Strength                                                                           Color                                                                             Angle                             __________________________________________________________________________    Cotton Printcloth                                                                      G     150° C 2 min                                                                   6       Crisp                                                                             Good White                                                                             90°                        PE/cotton Blend                                                               fabric 50/50                                                                           G     "       7       Good                                                                              Good White                                                                             45°                        Cotton Printcloth                                                                      H     "       19      Crisp                                                                             Good Yellow                                                                            135°                       PE/Cotton Blend                                                               Fabric 50/50                                                                           H     "       35      Crisp                                                                             Good Yellow                                                                            180°                       Cotton Printcloth                                                                      I     "       2       Good                                                                              Good White                                                                             45°                        Cotton Sateen                                                                          J     "       8       Good                                                                              Good White                                                                             90°                        PE/cotton Blend                                                               fabric 50/50                                                                           K     "       10      Good                                                                              Good Yellow                                                                            110°                       __________________________________________________________________________

We claim:
 1. A process for preparing a water soluble adduct polymercomprising:a. reacting a hydroxymethyl phosphorus compound selected fromthe group consisting of tris(hydroxymethyl)phosphine and tetrakis(hydroxymethyl) phosphonium hydroxide with a nitrogenous compoundselected from the group consisting of ammonia, hexamethylenetetramine,ethylenediamine and 1,6-hexamethylene diamine at a mole ratio of 1:4 to4:1 of amine to phosphorus compound to form an insoluble polymericprecipitate; and b. dissolving the precipitate from (a) in the presenceof formaldehyde and an inorganic or organic acid with a mole ratio of1:4 to 4:1 of formaldehyde to phosphorus contained in the precipitateand a 1:10 to 2:1 ratio of acid to phosphorus contained in theprecipitate.
 2. The product produced by the process of claim 1.